Method of combating insects and acarids with certain phenyl-carbamate derivatives



United States Patent METHOD OF COMBATIfiG INSECTS AND ACA- RIDS WITH CERTAIN PHENYL-CARBAMATE DERIVATIVES Horst Peissker, Wolfenbuttel, Albert Jiiger, Berlin- Hermsdorf, Walter Steinhausen, Grossburgwedel, and Gerhard Boroschewski, Berlin-Charlottenburg, Germany, assignors to Schering, A.G., Berlin, Germany No Drawing. Filed June 26, 1963, Ser. No. 290,586

Claims priority, application Germany, Aug. 2, 1962,

Sch 31,834 1 Claim. (Cl. 167-30) This invention relates to pesticides, and more particularly to novel carbamate derivatives which have insecticidal and acaricidal eifects.

We have found that compounds of the formula wherein R is lower alkyl or cyclohexyl; R and R are lower alkyl or jointly constitute a divalent radical which for-ms a fiveand six-member heterocyclic ring with the associated N atom containing in addition to said N atom only C atoms or an O atom and C atoms; R, and R are hydrogen, lower alkyl, lower alkenyl, or halogen; are effective agents for combating insect pests and spider mites which are plant parasites. The compounds of the invention and their salts with any suitable acid are capable of surprisingly long action when incorporated in pesticidal compositions.

Such compositions are highly efiective against a broad spectrum of pest insects. They may be employed to advantage where it is necessary to combat acarids and insects simultaneously, for example, in orchards, vineyards, truck. gardens, and hop fields, in cotton crops, and in other crops 3,336,186 Patented Aug. 15, 1967 in which insects may occur simultaneously with spider mites.

The compounds of the invention may be employed against pests in their pure 'form, in mixtures with each other and with other pest control agents such as acaricidal, insecticidal, or fungicidal compounds. They may constitute the active agents of compositions of all types commonly employed for the protection of crops against pests. Such compositions, in addition to the active agents, may contain liquid or solid inert carriers. Suitable liquid carriers table origin such as cotton seed flour or nut shell flour.

The composition may contain conventional auxiliary agents such as emulsifiers, wetting agents, binders, stabilizers, propellent gases, perfumes, pest attracting and pest repelling agents. The composition may be applied by dusting or otherwise spreading when they are solid. When liquid, they may be applied by fogging, spraying, or atomizing. The liquid compositions may be suspensions, emulsions, or solutions of the active agents, and may also be applied in the form of aerosols or -fumigants.

The percentage of active agents in the compositions may be varied Within wide limits. The concentration selected will depend on the type of composition, the method of application, the desired pesticidal effect, and particularly on the type of pest to be controlled. The content of active agents in the compositions of the invention will usually vary between 0.1 and 90 percent 'by weight. The composi-' tions are generally applied in concentrations between 0.025 and 10 percent. Under exceptional conditions, it may be necessary to apply them in concentrations as high as 20 percent.

Representative carbamate derivatives of the invention which have excellent insecticidal and acaricidal eifects are listed in Table 1 together with identifying physical properties. Where the formula of an acid radical appears 0 in conjunction with the name of its salt in Table 1, it

will be understood that the compoundis characterized by the melting point of its salt.

TABLE 1 (CH3)NCH=N O II I -O C-NH'CH: M.P. l02103 C.

' i n (CH;)iNCH=N- CNH-OHz M.P.82-0.

OH I a In cH, .N-oH=N-0oNH-om M.P.110C.

i w. c,m ,N-cn=N- 0-o-Nn oH. M.P.178-179O.

(hydrochloride) CHa II -V (0H3)iN-CH=NOCNHC:H:; on

CH=CH-CH;

II VI oH. ,N-cn=N- OCNHCH; -M.P.120-121C. (Chloraeetate) CH: v11. (0H,).N-oH=N-o-o-NH-cm M.P.156-157O.

IABLE 1-Con-tinued OH; (I) xxrv (CH3)zN-CH=NO-LNHC H M.P. ire-147 o.

H xXv l-.- Q-O-C-NH-om M.P.125C.

| N=CH--N(CH3)3 The following examples are illustrative of the biologi- Example 2 cal effects of the compounds of the invention.

Example 1 The residual effect of representative compounds of the invention was determined by treating bush bean plants in thelate two-leaf stage as described in Example 1. Other potted plants were infected for the first time 24 hours after treatment of the first group of plants and again at intervals of two to four days by placing spider mite infected leaves of the first group on leaves of the healthy plants. The mortality of the spider mites on the second group of plants seven days after infection by the applied leaves are tabulated in Table 3.

TAB LE 3 Com- Concentra- Residual effect on postembryonel stages atter pound tion of Number active agent,

percent 1 day 3 days 6 days 8 days 10 days 16 days I 0. 01 100 100 100 100 90 90 O. 005 100 100 95 100 90 40 III 0. 01 100 100 95 100 100 95 0. 005 100 100 100 60 80 80 VII 0. 01 100 100 100 100 100 100 on a rotating table. The amount of liquid applied was 50 Example 3 milliliters, and ensured wetting of the three plants contained in each pot until excess liquid dripped from them. The mortality of the postembryonal stages of the parasites after seven days was recorded in percent of the parasites present. The results are listed in Table 2.

TABLE 2 Concentra- Mortality of Mortality of Compound Number tion of adults and emerging active agent, nymphs, larvae, percent percent percent 0. 1 100 100 0.05 100 100 0.1 100 100 0.05 100 100 I (Hydrochloride) 0. 1 100 100 I Dih dro en hos hate 0. 1 1

y g p p 0. 100 100 II 0. 1 100 v 100 III 0.1 100 100 0.05 100 100 IV 0. 1 100 100 0. 05' 100 100 V 0. 1 100 100 0. 05 100 *100 VI 0. 1 100 100 0. 05 100 100 VII 0. 1 r r M 100 100 O. 05 100 100 VII (Lactate)- 0. 1 100 100 r "0. 05 100 100 VIII 0. 1 100 100 0.05 80 80 0.1 80 80 0. 1 100 e 100 0. 1 80 50 -0. 1 100 100 0. 1 100 100 XVI 0.1 100 100 XVII (p-toluene-sulfonate) 0.1 100 100 0.05 100 100 XVIII 0. 1 100 100 0. 05 100 100 XIX 0. 1 100 80 0. 05' 100' A 50 XXIII- 0. 1 90 90 XXV- 0. 1 100 100 0.05 100 100 The roots (a) or the stalks (b) of cut branches of bush bean plants free from parasites were placed in aqueous emulsions or salt solutions of several representative compounds of the invention when the'plants'were in the two-leaf stage. They were then infected by contact with leaves carrying spider mites,and a count of surviving parasites 48 hours after infestation gave the. results listed in Table 4.

TABLE 4 Concentration of Active agent,

percent Mortality of postelnbryonal stages after seven days, percent Compound Number (a) (Hydrochloride)-. ..llif.

III

VII

a ea ae O! k we (b) I (Hydrochloride) r cor 53 H03. 8 w

III

Example 4 Bush bean seeds were placed in recesses of clay dishes,

and the recesses were treated with solid mixtures of two parts of representative active agents of the invention and 98 parts kaolin. No unfavorable effects of the compounds of the invention could be observed in comparison tests between the treated seeds and untreated controls with respect to germination and growth. When the plants had reached the two-leaf stage, they were infected with moving spider mites in all postembiyonal stages by applica- TABLE 7 tion of leaves from infected plants. The mortality of the mites was determined after seven days, and the results Concentration Percentage obtained are listed in Table 5, Compound Number of active etlect alter agent, percent 24 hours 5 exposure TABLE 5 0.2 100 Compound Grams active Mortality of 3 Number agent per 100 g. postembryonal 2 75 seed material stages, percent 2 100 a. is 0. I g 28 0.02 100 0.2 100 VII 4 100 0,1 100 2 0. 100 0. 02 78 0.2 100 Example 5 8:5 8? VIII 0.2 100 Glass plates were treated with aqueous emulsions or 0.1 100 solutions of salts of the compounds of the invention in XI 8& 3% various concentrations. The liquid compositions were ap- 0.1 89 plied in amounts of 4 milligrams per square centimeter XV 8:3 8% by means of a spray gun having a glass nozzle at a pres- 0.1 85 sure of 0.5 kilogram per square centimeter. The liquid 82 P" 1 f 8:; 85 coatings were permitted to dry, and the plates were placed 0.1 94 as top covers on glass cylinders each containing 20 house flies (Musca domestica L), four days old. The flies were fed during the experiments with an untreated solu- Example 7 tion of sugar.

The effects of the compounds on the fli ft twenty The stomach and contact effects of the insecticidal comhours exposure were determined by counting the dead Pounds of the were deterfnlned treatlflg flies, the flies recognizably damaged and lying on th shoots of tradescantia on a revolving turntable with backs, and the flies surviving without visible symptoms. q o s emu sions suspensions, or salt solutions of thze The percentage effect of the various compounds of the compounds 0f the lnventlon amounts of 4 mg/cminvention was calculated according to Abbotts method. After drymg of e p yf coatlngs, the ifeated Plants The results obtained are listed in Table were each stocked in a Wire gauze cage with 15 fourthstage larvae of stick insects (Carausms morosus Brunner) which had recently shed their skins. The effects of the TABLE 0 compounds on the animals were evaluated daily by sepa- Concentmtion Percentage rate counts of dead animals, severely damaged animals Compound Number Active flectafter 40 which reacted to contact only by uncoordinated moveagenlipment ment of the extremities, slightly damaged animals, and normal animals. The results of the test are listed in I M 100 Table 8.

. 5 I (Hydrochloride) 0.2 100 TABLE 8 0.1 100 I (Lactate) 8-? $8 0 d N b Concentration Percentage 1 (Dihyd o e p osp at 3 1 3 um gifs giien. $5555 32?;

012 .52 0.2 0.1 100 I $3 tgg 05 100 I (Hydrochloride) 0. 1 100 0. 025 100 05 100 2 93 I (Lactate) 0. 1 100 0. 05 100 1 100 I (Dihydrogen-Phosphate) 0. 1 100 M 70 0. 05 100 (l2 g I11 0.1 100 Z 0. 05 100 68 0.025 100 0.2 100 0.2 100 M 97 68 0.1 100 80 0.05 100 0. 025 100 v1 (Chloracetate) o. 1 100 3- 28 Example 6 g: )5 h 00 The bottoms of Petri dishes were treated with various 0.1 100 concentrations of compounds of the invention in aqueous x 8'9 igg emulsions or as solutions of their salts at a dosage of 0: 05 100 4 milligrams per square centimeter. After drying of the X11 8: g3 liquid coatings, the dishes were stocked each with ap- XI 8.3 1 0 proximately 100 granary weevils (sitop'hilus granarius L.). v 1 1 After 24 hours exposure of the insects in a dark room XVII (Pmommesumnate) 86 igg in the open dishes, a differential count was made of 01025 93 weevils surviving without symptoms, dead weevils, and XIX 82% gg damaged weevils lying on their backs. The percentage XX 8.? 7g elfect was calculated according to Abbotts method, and XXI 1 the results are listed in Table 7. 27

TABLE 8C0ntinued Example 8 Tradescantia shoots were treated in the manner of Example 7 with aqueous emulsions or suspensions of active agents of the invention in uniform concentrations of 0.1 percent in amounts of 4 mg./cm. The plants were stocked at various times after treatment with 15 experimental animals as described in Example 7. The results obtained were evaluated in the same manner as in Exam- The pesticidal compounds of the invention which had not been known before were prepared in the following manner:

0.05 mole of a formamidinophenol was dissolved in a solvent such as tetrahydrofuran or in a mixture of 0.5 to 5 parts by weight of tetrahydrofuran and one part of dimet-hylformamide. The solution was mixed by shaking at room temperature with 0.05 mole of an alkyl or cycloalkylisocyanate. The reaction mixture was left to stand 48 hours at room temperature. Crystallization started during this time. The mixture was then heated to a boil for half an hour, and thereafter the solvent was distilled off in a vacuum.

The residue was either recrystallized from a mixture of benzene and petroleum ether or from a mixture of tetrahydrofuran and petroleum ether. In another purification method the residue was dissolved in benzene or chloroform and passed over a chromatographic column of neutral aluminum oxide. The products obtained were oily ple 7, and are listed in Table 9. in some cases, and were isolated either as oily liquids, or

' TABLE 9 Percentage efiect on plants stocked after- Compound Number 3 days 6 days 9 days 14 days 21 days 28 days 28 y VII 100 100 98 96 82 79 72 1 The treated plants were showered prior to the test with an amount of 15 liters per square meter within 45 minutes, and were stocked with test animals after air drying.

Example 9 Young oak shoots having approximately equal amounts of leaves were treated with 4 milligrams of a sprayed aqueous coating of emulsions or suspension of compounds of the invention per square centimeter. The spraying was performed on a turntable in the manner described above. After drying, the shoots were stocked with 10 caterpillars (L IV stage, immediately after shedding of skins) of the gypsy moth (Porthetriai dispar L.). The animals were retained in wire gauze cages. The effects of the pesticidal compounds were determined daily, and the efficiency was evaluated as described in Example 8. The percentage effects achieved after three days with representative compounds of the invention are listed in Table 10.

TABLE 10 Concentration of active agent, percent P ercentage efiect Compound No.

after 3 days 0OHNOOOHNOOHNOHNOOl-NHNOHN NM r gor tom an HO! XVI in the form of their crystallized solid salts, such as the hydrochloride, the lactate, the p-toluenesulfonate, or the chloracetate.

The following examples will illustrate the method of preparing the, carbamate derivatives of the invention.

Example 10 32.84 grams (0.2 mole) of 3-(N,N-dimethylaminomethylenimino)-phenol were dissolved in a mixture of milliliters tetrahydrofuran and 120 milliliters dimethylformamide, and the solution was left to stand 48 hours at roomtemperature. It was subsequently heated to a boil for 30 minutes, and the solvent mixture was evaporated in a vacuum. The oily residue was dissolved in chloroform, and filtered over aluminum oxide (neu t-ral). After evaporation of the chloroform in a vacuum, the residue was crystallized in the presence of a small amount of ether, and was recrystallized from ethyl acetate. The yield was 26.6 grams (60%), the melting point 102-103 C.

The elementary analysis corresponded to that of the COmPOund C11H15N302.

Calculated: C, 59.70; H, 6.83; N, 18.99. Found: C, 59.88; H, 7.14; N, 19.06, which is N-methyl-3-(N',N- dimethylaminomethylenimino)-phenylcarbamate.

The phenols which were employed as starting materials for preparing the pesticidal agents of the invention were prepared as follows:

0.1 mole of a suitably substituted aminophenol was dissolved either in 25 milliliters dimethylformamide or in another suitable, solvent, such as acetonitrile, in the presence of 0.1 mole dimethylformamide; 9.15 milliliters phosphorus oxychloride were added drop by drop with agitation while the temperature was held at or below 60 C. by means of external cooling. After completion of the phosphorus oxychloride addition, the mixture was agitated for 30 additional minutes at 60 C. When ethanol was added and the mixture was cooled to room temperature, crystallization of the desired hydrochloride usually occurred very rapidly. If necessary, crystallization was made more complete by addition of ethyl ether.

If the hydrochloride obtained was not satisfactorily pure, it was recrystallized from ethanol or from a mixture of ethanol and ether. It was then dissolved or suspended in water, and an equivalent amount of a strong base 1 1 such as triethylamine, NaOH or Na CO was added whereupon the free phenol crystallized. If necessary the aminophenol was recrystallized from a mixture of tetrahydrofuran and alight petroleum fraction.

The pesticidal compounds of the invention may also be prepared by reacting a corresponding phenol with a mono-substituted car-b'amic acid chloride in a manner well known in itself.

While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not limited thereto, but is to be construed broadly, and restricted solely 'by the scope of the appended claim.

We claim:

A method of combating insects and acarids which comprises contacting said insects and acarids with a pesticidal amount of a compound of the formula wherein R is selected from the group consisting of lower alkyl and cyclohexyl; R and R are lower alkyls and R and R together with the nitrogen atom is a heterocyclic ring selected from the group consisting of five member and six-member heterocyclic rings containing in addition to said nitrogen atom only carbon atoms, and of six-member heterocyclic rings containing in addition to said nitrogen atom an oxygen atom and carbon atoms; and R and R are members of the group consisting of hydrogen, :lower alkyls, lower alkenyls, and halogen.

References Cited UNITED STATES PATENTS 2,984,682 5/1961 Kaeding 260479 3,012,068 12/1961 Shulgin 260482 3,071,506 1/1963 Gruenhagen 16733 3,072,648 l/l963 Bonvicino 260-240 3,072,649 1/1963 Semb et al 260-240 3,080,279 3/ 1963 Constantin et al 167-33 ALBERT T. MEYERS, Primary Examiner.

LEWIS GOTTS, JULIAN S. LEVITT, Examiners.

G. A. MENTIS, R. S. BARRESE, Assistant Examiners. 

